A Very Brief Introduction to Infrared Spectroscopy © ABB Group April 29, 2019 | Slide 1

Basics of the Technique © ABB Group April 29, 2019 | Slide 2

Infrared Spectroscopy The term “Infrared Spectroscopy” simply means the study matter using Infrared Radiation. Matter is the “stuff” everything is made of. Matter is composed of molecules Water Molecule Infrared Radiation is composed of waves of light that are just beyond the range that is visible with our eyes. © ABB Group April 29, 2019 | Slide 3

Molecular Vibrations The molecules that make up matter are vibrating all time. The bonds that hold the molecules together are stretching and bending thousands of times a second. For example the water molecules in the air in this room is vibrating right now. Each type of molecule and type of vibration has a unique frequency. For example the frequency of the stretch vibration of a bond of Carbon and Oxygen like in Carbon Dioxide is stretching about 51,500000,000000 times in each second. © ABB Group April 29, 2019 | Slide 4

Infrared Radiation Light can also be measured in frequency ( just like with the number of vibrations in a second for molecular bonds) With frequencies of light we use the term wavenumber per centimeter this is the number of waves of the light that fit into each centimeter. 1cm For example the frequency of this wave is 1cm-1 The infrared source in an infrared spectrometer creates infrared radiation of many different frequencies at the same time just like a light bulb creates many different frequencies of visible light. © ABB Group April 29, 2019 | Slide 5

Interaction of Light with Matter If the frequency of the infrared light matches the frequency of the vibration in the bond of the molecule than the molecule absorbs some of the light. Sample Incident IR Beam Remaining IR Beam Infrared Source Detector © ABB Group April 29, 2019 | Slide 6

Infrared Spectrum Recording a spectrum is a little like tuning in to radio stations... We scan through all the frequencies (like turning a tuning knob) At certain frequencies the infrared light is absorbed by a molecular vibration (we hear music) Sometimes the signal is strong, sometimes weaker (the peak is higher or lower) Sometimes we hear nothing at all! 0.2 0.4 0.6 0.8 1.0 4000 3000 2000 1000 Absorbance spectrum of the sample ( polystyrene film ) Strength of signal Scanning through frequencies © ABB Group April 29, 2019 | Slide 7

Interpreting Spectra The position of the peak (frequency of absorption) tells us what type of molecular vibration we have and so can help to indentify what material we have The size of the peak (the amount of light absorbed) tells us how many of those vibrations are there and so can tell us the concentration of a substance Note: This spectra is shown as a transmittance rather than and absorbance spectra thus the peaks the opposite way up © ABB Group April 29, 2019 | Slide 8

Infrared spectroscopy – Mid or Near Mid-infrared (FT-IR) Strong absorption Mainly used for qualitative analysis Difficult to accurate control very small pathlengths Classical laboratory technique Direct chemical interpretation (band separation) Simple calibrations (“peak height” models) Difficult on process, cannot pass through glass and requires very small samples Sensitive, can detect ppm levels Near-infrared (FT-NIR) Overtone and combination bands- Echoes of the MID IR bands Weaker absorption Not sensitive, concentrations need to be above 0.5% Mainly C-H, O-H, N-H vibrations Can be used for qualitative and quantitative analysis Contains chemical and physical information Well suited to process No direct chemical interpretation Calibrations requires “chemometrics” to help get the information out of the spectra 1st Overtone .. Combination.. Fundamental NIR Mid-IR Frequency Note: The same information is repeated in Mid-IR and NIR. In can be helpful to think of NIR spectra as the echo’s of the Mid IR spectrum

Calibration © ABB Group April 29, 2019 | Slide 10

Calibration Building a model Using a model Infrared spectroscopy is generally not a primary technique of determination of physical and chemical properties. The infrared Analyzer must be calibrated. We “train” the instrument using reference data from primary analytical method or using samples made from primary materials and methods. Building a model Using a model Concentration, viscosity property data on each spectrum Single sample infrared Spectra Primary techniques use either primary standards or primary principles e.g.. titrations/ gravimetric methods) Usually the customer provide the reference data and ABB performs and validates the calibration Calibration Model Calibration Model Multiple infrared Spectra Concentration, viscosity property prediction on the sample spectrum © ABB Group April 29, 2019 | Slide 11

Instruments © ABB Group April 29, 2019 | Slide 12

Lab - Platforms Platform MB-Series Wavelength Range (Mid or Near) MB3600-HP10 MB3600-CH20 MB3600-CH40 MB000-PH MB3000-CH60 MB3600-CH50 Industry or Application Specific Product MB3600-CH30 MB3600-CH10 MB3600-PH MB-RX © ABB Group April 29, 2019 | Slide 13

Process Platforms Remote, fibre optic systems – Highly Flexible Extractive systems– Specialist applications Platform FTPA2000-300 Series FTPA2000-460 Series FTPA2000-260 TALYS TALYS ASP310 TALYS ASP521 FTPA2000-HP20 FTPA2000-HP260 FTPA2000-300 FTPA2000-304 FTPA2000-HP460 FTPA2000-HP40 TALYS ASP501 TALYS ASP531 FTPA2000-260PH FTPA2000-HP260X FTPA2000-300T FTPA2000-304T FTPA2000-HP50 TALYS ASP511 TALYS ASP541 FTPA2000-260SC3 FTPA2000-260SC8 Industry or Application Specific Product FTPA2000-360 FTPA2000-HP360 FTPA2000-PT260 FTPA2000-360T FTPA2000-HP41 FTPA2000-304 FTPA2000-HP51 © ABB Group April 29, 2019 | Slide 14

General Summary FTPA2000-260 MB3000 MB3600 TALYS Others Fibre Optic process Near Infrared Analyser (Single or Multichannel) Other specialist instruments usually for specific HPI applications Mid Infrared Lab Analyser for Qualitative analysis Near Infrared Lab Analyser for Quantitative analysis © ABB Group April 29, 2019 | Slide 15

Sampling Methods © ABB Group April 29, 2019 | Slide 16

Hardware Configuration The hardware for an infrared application is composed of an instrument platform and a sampling accessory to introduce the sample to the instrument Sample Incident IR Beam Remaining IR Beam Infrared Source Detector Instrument Sample Accessory © ABB Group April 29, 2019 | Slide 17

Laboratory- MB3000/MB3600 Sample Compartment Infrared light passes from the source passes through the sample and is collected by the detector. ABB offers a range of accessories that fit into the sample compartment depending on the nature of the sample Source Detector © ABB Group April 29, 2019 | Slide 18

Process - Fibre Optic Remote Spectrometers Infrared light output through fibre optics Source Sample Compartment Detector Infrared light returned through fibre optics Infrared light passes from the source through a glass fibre to the sampling accessory. Once interacted with the sample the remaining light is passed back though another fibre back to the instrument detector. NIR only as Mid IR will not pass through the glass fiber © ABB Group April 29, 2019 | Slide 19

Transmission In a transmission measurement the sample is simply placed directly into the infrared beam between the source and detector. Transmission measurement can be carried out on solids, liquids and gases. Sample Incident IR Beam Remaining IR Beam Infrared Source Detector Sample “Pathlength”, this is the thickness of the sample measured. The greater (the thicker the sample) the pathlength the more infrared radiation is absorbed. So different measurements will need different pathlengths. As Mid-IR has stronger absorption the pathlengths need to be more smaller or all the radiation will be absorbed and none will reach the detector © ABB Group April 29, 2019 | Slide 20

Transmission – Example Accessories Vial Holder - Lab Accommodates 3 vial diameters for 3 mm, 5 mm and 10 mm pathlengths. NIR only Liquid Cell - Lab Two windows with a controlled sample gap. Pathlengths from a few microns (Mid IR) to several mm (NIR) NIR and MIR Flow Cell - Process Path lengths from 1mm to 10mm Wide range or pipe interface diameters and materials NIR only © ABB Group April 29, 2019 | Slide 21 © ABB Group April 29, 2019 | Slide 21

Diffuse Reflectance Infrared Source Detector Remaining IR Beam Diffuse reflectance allows for the measurement of a wide range of solid samples such as surface coatings, powders, paint chips etc. The incident bema is directed at the sample and a portion of the reflected light is measured by the detector. Can be used in the Mid and NIR but mainly used in the NIR. © ABB Group April 29, 2019 | Slide 22

Diffuse Reflectance – Example Accessories Powdir Samplir- Lab Measures the sample held in a glass vial Can rotate to better average the sample NIR only Diffuse Reflectance Probe- Lab or Process Various versions available for use with laboratory or process instruments NIR only © ABB Group April 29, 2019 | Slide 23

Attenuated Total Reflection (ATR) The infrared beam is reflected inside a reflecting crystal of high refractive index When it hits the crystal-air interface the infrared radiation extend fractionally outside of the crystal The sample in contact with the crystal will then absorb some radiation as it would with other methods and the remaining portion of the light is directed to the sample The ATR accessory can use a single reflection or many (e.g. 10) the more reflections the greater the pathlength through the sample Difficult to accurately reproduce the pathlength so ATR is mainly for qualitative analysis (identification). ATR Crystal Infrared Source

ATR – Examples Miracle Single Bounce ATR – Lab Can be used for all types of solids and liquids Usually a Diamond or ZnSe Clamp used for solids to get good contact with ATR Mid-IR only ATR Probes – Lab and Pilot Plant To be used with liquids Usually a Diamond or ZnSe Come with special mid-IR fibres (only for use over short distances) Mid-IR only © ABB Group April 29, 2019 | Slide 25

Software © ABB Group April 29, 2019 | Slide 26

Software Horizon QA Horizon MB FTSW100 Laboratory Process Workflow software. Controls the analyser settings and holds a configuration to allow rapid acquisition of results by an operator though simple onscreen prompts. Manages historical data and generate reports. Spectral viewing and interrogation software. Has multiple optional modules to add extra functionality. E.g “Quantify module” for building calibration models. Aimed more at the skilled user. A ground up dedicated process control software. For a Near Infrared instrument. Manages all aspects of data acquisition, data handling, I/Os, DCS integration, alarms, reporting and analyser diagnostics. © ABB Group April 29, 2019 | Slide 27